4-benzoyl-1-alkyl (alkenyl) - pyrazoles, composition containing them, herbicidal method of using them, and intermediate in their preparation

ABSTRACT

Pyrazole derivatives of the formula I: ##STR1## wherein R represents a lower alkyl group or a lower alkenyl group atoms which may be substituted by halogen atom, 
     X represents a halogen atom, a lower alkyl group, nitro group, cyano group, a lower alkylsulfonyl group or trifluoromethyl group, 
     n is an integer of 2 to 4, 
     Q represents hydrogen atom; an aralkyl group which may be substituted by halogen atom, nitro group, cyano group or a lower alkyl group; benzenesulfonyl group which may be substituted by a lower alkyl group or halogen atom; benzoyl group which may be substituted by a lower alkyl group or halogen atom; phenacyl group which may be substituted by a lower alkyl group or halogen atom; a lower alkyl group which may be substituted by halogen atom; a lower alkenyl group which may be substituted by halogen atom; or a lower alkynyl group, 
     and a method for preparation of said derivatives, a selective herbicidal composition containing said derivatives as active ingredient, 
     as well as a method for controlling weeds using said derivatives.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to novel pyrazole derivatives, method for preparation thereof, a selective herbicidal composition containing as an active ingredient one or more of said derivatives, and method for damaging and controlling weeds using said derivatives.

(2) Description of the Prior Art

Hitherto, some pyrazole derivatives having herbicidal activity have been known. For example, Japanese Patent Publication No. 36648/79 (corresponding to U.S. Pat. Nos. 4,063,925 and 4,146,726) and Japanese Laid-open Patent Publication No. 41872/79 (corresponding to U.S. Pat. No. 4,230,481), Japanese Laid-open Patent Publication No. Sho 56-61358 (61358/81), U.S. Pat. No. 4,557,753 and U.S. patent application Ser. No. 735,656 disclose certain 4-benzoyl derivatives of pyrazole which are useful for herbicides.

Among these pyrazole derivatives, however, two compounds represented by the formula below are used practically and commercially as an active ingredient of a herbicide for use in a paddy field as far as the present inventors' knowledge is concerned. ##STR2##

All the pyrazole derivatives disclosed by the above-mentioned publication No. 41872/79 have a lower alkyl group, specifically CH₃ group, at 3-position of the pyrazole ring.

Also the majority of the pyrazole derivatives disclosed by the above-mentioned publication No. 36648/79 have a lower alkyl group at the 3-position of the pyrrazole ring and --OH, --SH, a salt thereof or an organic acid ester thereof at 5-position of said ring; among the pyrazole derivatives disclosed by said publication, only the compound of the following formula is exemplified as a pyrazole derivative having hydrogen atom at 3-position (i.e., unsubstituted at 3-position) of the pyrazole ring: ##STR3##

The compound C, however, is inferior to the commercialized compound A in herbicidal activity as is apparent from the biological test data given in the above-mentioned publication No. 36648/79.

Despite the fact that a number of pyrazole derivatives have been synthesized and the herbicidal activity thereof has been tested, there has not been found a pyrazole derivative which is unsubstituted at 3-position of the pyrazole ring and which exhibits herbicidal activity except the above-mentioned compound C.

This is because synthesis of pyrazole derivatives unsubstituted at 3-position has been very difficult while a pyrazole derivative substituted by an alkyl at 3-position has been relatively readily prepared, and because the former compound has been believed to be less active in herbicidal action and thus less practical than the latter one.

The present inventors have done intensive research on pyrazole derivatives having hydrogen atom at 3-position of the pyrazole ring and have unexpectedly found that some of these pyrazole derivatives exhibit herbicidal action against a wide range of weeds, particularly against perennial weeds such as perennial flat sedge (Cyperus serotinus), bulrush (Scirpus juncoides) and perennial spikerush (Eleocharis kuroguwai) which have been difficult to control and against which no useful herbicide has been developed. Moreover, the present inventors have found a process for readily preparing such 3-H pyrazole derivatives to complete the present invention. The 3-H pyrazole derivatives have no phytotoxicity upon a paddy-rice plant and, thus, can be used with safety.

The present inventors have filed an application for an invention on the basis of the above-mentioned knowledge and have been granted a patent thereto under the U.S. Pat. No 4,557,753,. In this U.S. Pat. No. 4,557,753, the pyrazole derivatives have hydrogen atom at 3-position of pyrazole ring, CH₃ group at 1-position thereof and a specific substituent group at 5-position thereof.

After the present inventors have intensively advanced the researches, they have found that in the above-mentioned 3-H pyrazole derivatives, when 1-C₂ H₅ compounds having an ethyl group at 1-position of pyrazole ring and 1-CH₃ compounds having methyl group at the same position are compared, 1-C₂ H₅ compounds showed remarkable effectiveness against to the grass weeds, and the improvement of the effectiveness against to the paddy weeds as Monochoria vaginalis, Alisma canaliculatum has reached to more than ten times as the effects of 1-CH₃ compounds, which has been way above the initial expectation.

Among the compounds according to the present invention, there exist some compounds which show superior safety to cultivated plants, e.g., rice (Oryza satva), or show very high safety to corn (Zea mays) in the dry field farming, while some compounds show remarkable improvement of the effectiveness against to grass weeds in the field of corn (Zea mays), yellow nutsedges (Cyperus esculeutus) and broadleaf-weeds in comparison with that of 1-CH₃ compounds.

Moreover, in comparison with prior art compound, the specificity of substitution at 1-position of prazole ring which is the features of the present invention is summed up as follows:

Firstly, in case of 3-CH₃ type pyrazoles as recognized in the earlier patent application, U.S. Pat. No. 4,063,925, and as apparent from the comparison between the compounds of said U.S. Pat. No. 4,063,925: Compounds No. 44 and No. 11, Compounds No. 107 and No. 51, Compounds No. 108 and No. 14, and Compounds No. 109 and No. 105, it is clear that the intention of said U.S. Pat. No. 4,063,925 was directed to 1-CH₃ compounds because there was no remarkable difference of activity between 1-CH₃ type pyrazoles and pyrazoles substituted by alkyl group having more than two carbon atoms at 1-position (under the both conditions of paddy field and dry field farming).

On the other hand, in case of 3-H type pyrazoles, as shown in the later-described tables, there was remarkable difference of activity between 1-CH₃ compounds and pyrazoles substituted by alkyl group having more than two carbon atoms at 1-position. In this aspect, it is understood that even a person skilled in the art could not expect the present invention.

Especially, under not only paddy-rice field conditions but also dry field farming, the present invention has such as inventive step that the present invention shows remarkable higher activity is not only soil treatment but also foliage application which show very high cultivated plant-selectivity. Furthermore, the present invention has sufficient inventive step in a point that it shows higher activity with respect to seriously harmful weeds such as grass weeds, broadleaf-weeds, etc., and further to Cyperus esculeutus, yellow nutsedge. Also, Japanese Laid-open Patent Publication No. Sho 56-61358 (61358/81), one of the prior arts, shows herbicidal activity of pyrazoles having methyl group at 3-position under the paddy-field conditions. In said Japanese Laid-open Patent Publication, the compound No. 4 has isopropyl group at 1-position. However, comparing with the compounds No. 2, No. 3 and No. 5, all having methyl group at 1-position, said compound No. 4 has lower activity. As aforementioned, in the 3-methyl type pyrazoles, the substituent of more than 1-C₂ has no superior properties in comparison with 1-methyl compounds. Thus, it shows that the fact that in 3-H type pyrazoles, the superiority of having a substituent have more than C₂ at 1-position instead of a methyl group could not be expected. At the same time, in said Japanese Laid-open Patent Publication, only applicability to the rice-field conditions was described. Therefore, the safety of the present compounds to economic plants, corn (Zea mays) included and applicability of the present compounds to the dry-field farming can not be expected from said Japanese Laid-open Patent Publication.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel pyrazole derivative having strong herbicidal action against weeds, particularly against weeds in paddy field which have not been easily controlled.

Another object of the present invention is to provide a process for preparing the above-mentioned novel pyrazole derivatives.

Further object of the present invention is to provide a selective herbicidal composition containing one or more of such pyrazole derivative(s) as an active ingredient.

Still further object of the present invention is to provide a novel pyrazole derivative which can control weeds in the field of corn. Among the compounds of the present invention, there are compounds which are very high as to safety to corn (Zea mays) and have also very strong activity against various kinds of weeds such as grass weeds, Cyperus esculeutus, yellow nutsedge, broadleaf-weeds, etc. in the field of corn; especially these compounds show high effects in controlling grass weeds at the vegetation period, which provide controlling technology which has not been accomplished by the conventional chemicals.

Other objects and features of the present invention will be apparent from the description hereinbelow.

DETAILED DESCRIPTION OF THE INVENTION

Pyrazole derivatives of the present invention are represented by the formula I: ##STR4## wherein

R represents an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms which may be substituted by halogen atom,

X represents a halogen atom, a lower alkyl group, nitro group, cyano group, a lower alkylsulfonyl group or trifluoromethyl group,

n represents an integer of 2 to 4,

Q represents hydrogen atom; an aralkyl group which may be substituted by halogen atom, nitro group, cyano group or a lower alkyl group; benzenesulfonyl group which may be substituted by a lower alkyl group or halogen atom; benzoyl group which may be substituted by a lower alkyl group or halogen atom; phenacyl group which may be substituted by a lower alkyl group or halogen atom; a lower alkyl group which may be substituted by halogen atom; a lower alkenyl group which may be substituted by halogen atom; or a lower alkynyl group.

Preferable substituents R are ethyl group, isopropyl group or allyl group; and most preferable ones are ethyl group or isopropyl group.

Preferable substituents X at 2- and 4-positions are halogen atom, lower alkyl group, nitro groups, lower alksulfonyl group and trifluoromethyl group; and in case that they are unsubstituted, activity is generally lowered. Preferable substituents X at 3-position are lower alkyl group and halogen group, but this position may be unsubstituted. The most preferable substituents X are halogen atom including chlorine atom or methyl group, in 2-position; non-substitution or methyl group, at 3-position; and halogen atom including chlorine atom and methanesulfonyl group, in 4-position.

In case that Q to does not represent a hydrogen atom, Q is one of various substituents, which shows an activity having basically the same property as compounds in which Q is hydrogen. However, by introducing substituents into Q, there may often cause such cases that strongness or weakness of acitivity and weeding sprectrum change; especially there may be a case that phytotoxicity to economic plants are further lowered. The above-mentioned substituents are selected from various kinds of substituents. In light of herbicidal activity, safety to the economic plants and ready production of compounds. The most preferable substituents are hydrogen atom, benzyl group, p-toluensulfonyl group, phenacyl group, methanesulfonyl group, acetyl group.

Preferred compounds of the formula I are those wherein R represents an alkyl group having 2 to 4 carbon atoms or allyl group, X represents a halogen atom, a lower alkyl group, nitro group, a lower alkylsulfonyl group or trifluoromethyl group, n is an integer 2 to 4, and Q represents benzyl, tosyl, methanesulfonyl, benzoyl, phenacyl, allyl, propargyl group or hydrogen atom.

Other preferred compounds of the formula I are those wherein R represents ethyl or isopropyl group, X represents a halogen atom, a lower alkyl group or methanesulfonyl group, n is an integer 2 to 4, and Q represents hydrogen atom, benzyl, tosyl, mesyl, phenacyl, allyl or propargyl group.

More preferred compounds are those of the formula V: ##STR5## wherein R represents ethyl or isopropyl group, and Q represents hydrogen atom, benzyl or phenacyl group.

Particularly preferred compounds are those of the formula VI: ##STR6## wherein R represents ethyl or isopropyl group, X represents methyl group or chlorine atom and Q represents hydrogen atom or benzyl group.

More especially preferred compounds are those of the formula VII: ##STR7## wherein R represents ethyl or isopropyl group, X represents methyl group or chlorine atom and Q represents hydrogen atom or benzyl group.

Compounds having the best combinations of R, X and Q are:

4-(2,4-dichlorobenzoyl)-1-ethyl-5-benzyloxypyrazole,

4-(2,4-dichlorobenzoyl)-1-isopropyl-5-benzyloxypyrazole,

4-(2-chloro-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole

4-(2-chloro-3-methyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole

4-(2-chloro-4-methanesulfonylbenzoyl)-1-isopropyl-5-hydroxylpyrazole

4-(2-chloro-3-methyl-4-methanesulfonylbenzoyl)-1-isopropyl-5-hydroxypyrazole

4-(2-methyl-4-methanesulfonylbenzoyl)-1-ethyl-5-hydroxypyrazole

4-(2-methyl-4-methanesulfonylbenzoyl)-1-isopropyl-5-hydroxypyrazole

4-(2,3-dimethyl-4-methanesulfonyl)-1-ethyl-5-hydroxypyrazole

4-(2,3-dimethyl-4-methanesulfonylbenzoyl)-1-isopropyl-5-hydroxypyrazole

The compounds of the formula I may be readily prepared according to the following reaction scheme: ##STR8## wherein

Z represents a halogen atom or hydroxyl group, preferably chlorine,

Hal represents a halogen atom, preferably chlorine or bromine, and R, X, Q and n each have the same meanings as defined in formula I.

Reaction (1) represents a reaction series comprising (i) synthesizng 4-carboethoxy-5-hydroxy-1-alkyl(alkenyl)pyrazole from a diethyl ethoxymethylene malonate and alkyl(alkenyl)hydrazine through cyclization reaction, followed by (ii) hydrolyzing with mineral acid such as hydrochloric acid, etc. and decarboxylating the resulting compound to obtain 5-hydroxy-1-alkyl(alkenyl)-pyrazole. The cyclization reaction is performed at a temperature from -50° C. to 200° C., preferably from -20° C. to 100° C. in an inert solvent such as methanol, ethanol, water, dioxane, benzene or toluene.

The hydrolysis and decarboxylation is performed at a temperature from 50° C. to 150° C., preferably around boiling point of the solvent used in cyclization reaction. All of compounds (a) which are an intermediate of the present invention are novel substances and group of compounds which can be utilized as an intermediate for medicine and agricultural chemicals. In this connection, the compound (a) is a tautomer with a compound (a') shown by the following formula (a'): ##STR9## The compounds (b) can be prepared from compound (a) as a starting material through, for example, Reaction (2). For example, compounds (b) may be prepared by reacting compound (a) with a substituted benzoyl halide in an inert solvent in the presence of a dehydrohalogenating agent, preferably such as sodium hydroxide, potassium hydroxide, sodium carbonate or triethylamine to produce the corresponding esters and then effecting rearrangement of the esters to obtain the compounds (b). As the solvent for the esterification reaction may be used, for example, organic solvents such as dioxane, acetonitrile, benzene, toluene or chloroform alone or in combination with each other or with water, namely two phase systems such as water-toluene, water-chloroform and the like. Preferred solvents, however, for the esterification are water-chloroform two phase system. The rearrangement of the ester is performed by heating the ester with potassium carbonate or sodium carbonate in an inert solvent such as doxane at a temperature from 50° C. to 150° C.

Instead of Reaction (2), the compound (b) may readily be synthesized by Reaction (2)': ##STR10##

According to this reaction, the objective compound (b) can be obtained readily and in a good yield in one step by reacting the compound (a) with appropriate substituted benzoic acid under the presence of an appropriate condensing agent and a basic substance.

As a dehydrating condensing agent used in this reaction, carbodiimides such as N,N'-dicyclohexyl carbodiimide, N,N'-diisopropyl carbodiimide N,N'-diethyl carbodiimide, N-cyclohexyl-N'-morpholinoethyl carbodiimide are suitable.

Suitable basic substances are, for example, sodium carbonate, potassium carbonate, sodium methoxide, potassium ethoxide and potassium-tertiary-butoxide.

Furthermore, this reaction is carried out in an inert solvent. For example, it is desirable to use alcohols such as isopropanol, tert.-butanol, sec-butanol, tert.-amylalcohol, but ketones such as methylethyl ketone, diethyl ketone, etc. and nitriles such as acetonitrile, propionitrile, etc. may be used.

The reaction is completed between 30 minutes and 10 hours by mixing the compound (a), substituted benzoic acid, dehydrating condensing agent having equal mole, a basic substance having a half to equal mole in the solvent and heating the mixture. The reaction temperature is not especially limited, but is desirable to determine the temperature between 50° C. and a boiling point of a solvent to be used.

After the reaction, the objective compound (b) is obtained in the form of metal salt. Moreover, the compound (b) which is the free form can be readily isolated by using appropriate acid to adjust pH to <3.

Reaction (3) represents a condensation reaction of an intermediate (b) with an appropriate halide such as benzyl chloride or tosyl chloride to produce the compound of the formula I. This reaction is preferably carried out in a solvent which is inert to the reaction in the presence of a dehydrohalogenating agent. Suitable inert solvents are, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methylethyl-ketone, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethyl acetate, N,N-dimethylformamide, acetonitrile and the mixtures thereof. Among these solvents preferred ones are benzene, toluene, acetone and acetonitrile. Suitable dehydrohalogenating agents for Reaction (3) are, for example, inorganic bases such as sodium carbonate, and potassium carbonate, and organic bases such as pyridine, triethylamine and N,N-diethylaniline, and preferably triethylamine. The reaction temperature ranges from room temperature to the boiling point of the solvent employed. However, it is most advantageous to effect the reaction at the boiling point of the solvent from the viewpoint of operation. By selecting the above-mentioned reaction conditions of the condensation reaction (3) appropriately, the compounds of the formula (I) can be obtained in a quite high yield.

Synthesis of the compounds according to the present invention is illustrated by way of the following examples which do not restrict the present invention.

SYNTHESIS EXAMPLE 1 Synthesis of 1-ethyl-5-hydroxypyrazole

A solution of 10.8 g (0.05 mol) of ethoxymethylenemalonate diethyl ester in 20 ml of ethanol was cooled to 0° C. To the solution was added dropwise 10 g (0.05 mol) of 30% aqueous solution of ethylhydrazine, while keeping the reaction temperature at below 5° C. After the completion of the dropwise addition, the resulting mixture was stirred for 1 hours at room temperature, and then refluxed for 3 hour. After the completion of the reaction, the solvent in the mixture was distilled off under reduced pressure and concentrated. Then, the residue was added with 20 ml of 35% hydrochloric acid and was subjected to hydrolysis and decarbonating reaction at the reflux temperature for 3 hours. After the completion of the reaction, the solvent was distilled off under the reduced pressure and dried to obtain 5.3 g of 1-ethyl-5-hydroxy-pyrazole as its hydrochloride.

Yield: 72%

¹ H-NHR (δ, ppm, CDCl₃ -DMSO-d₆): 1,42 (3H, t, J=7 Hz, CH₃), 4.20 (2H, q, J=7 Hz, CH₂ --CH₃), 5.91 (1H, d, J=3 Hz, pyrazole), 7.84 (1H, d, J=3 Hz, pyrazole), 12.4 (2H, broad s)

SYNTHESIS EXAMPLE 2 Synthesis of 4-(2,4-dichlorobenzoyl)-1-ethyl-5-hydroxypyrazole

To an aqueous solution of 13.2 g (0.2 mol) of potassium hydroxide (pure degree: 85%) dissolved in 55 ml of water was portionwise added 14.85 g (0.1 mol) of 1-ethyl-5-hydroxy-pyrazole hydrochloride with stirring under the ice cooling and neutralized to obtain its potassium salt. Thereafter, 60 ml of chloroform was added to the reaction mixture to prepare two layers. In the resulting mixture was dropwise added 20.95 g (0.1 mol) of 2,4-dichlorobenzoyl chloride while keeping the temperature at below 5° C. and the mixture was stirred at room temperature for 2 hours, followed by addition stirring for 1 hour at 40° C., and then, the reaction was ceased. After cooling the reaction solution, the organic layer was separated, washed successively with 5% aqueous sodium bicarbonate, water and saturated brine and, after drying over sodium sulfate anhydride, the solvent was distilled off under reduced pressure and the remaining mixture was dried and caked to give a crude product of 5-(2,4 -dichlorobenzoyloxy)-1-ethylpyrazole. Then, thus obtained ester-form crude product was added with 10 ml of 1,4-dioxane and dissolved, and was added with 20.7 g (0.15 mol) of anhydrous potassium carbonate at 120° C. The resulting mixture was continued to heat with stirring for about 1 hour to solidify the reaction mixture. The obtained solid product was added with 50 ml of water and heated to be dissolved. After the dissolution, the temperature was cooled to the room temperature, and the dissolved mixture was added with hydrochloric acid to adjust to pH <1. The precipitated solid product which was obtained by filtration was dried and and recrystallized from a mixture of n-hexane-benzene to obtain 22.5 g of 4-(2,4-dichlorobenzoyl)-1-ethyl-5-hydroxypyrazole.

Yield: 79%

m.p.: 144°-146° C.

¹ H-NMR (δ, ppm, CDCl₃): 1.43 (3H, t, J=7 Hz, --CH₃), 4.04 (2H, q, J=7 Hz, --CH₂ --), 7.30-7.47 (4H, m), 9.57 (1H, S, --OH)

SYNTHESIS EXAMPLE 3 Synthesis of 4-(2,4-dichlorobenzoyl)-1-ethyl-5-benzyloxypyrazole

To 30 ml of benzene was added 1.43 g (0.005 mol) of 4-(2,4-dichlorobenzoyl)-1-ethyl-5-hydroxypyrazole and additionally added 0.51 g (0.005 ml) of triethylamine to prepare homogeneous solution.

To the solution was added 0.86 g (0.005 mol) of benzyl bromide with stirring at the room temperature and then, heated and reacted at the reflux temperature for 4 hours. After the reaction mixture thus obtained was cooled, the prepared salt was filtered off. The obtained benzene solution was washed successively with 5% aqueous solution of sodium bicarbonate, water and saturated brine, and dried with anhydrous sodium sulfate. Then, the benzene was distilled off under reduced pressure to give oily residue. The resulting oil was purified through a silica gel column chromatography (eluent:benzene) to obtain 1.41 g of the objective 4-(2,4-dichlorobenzoyl)-1-ethyl-5-benzyloxypyrazole as colorless oily product.

Yield: 75%

¹ H-NMR (δ, ppm, CDCl₃): 1.19 (3H, t, J=7 Hz, --CH₃), 3.83 (2H, t, J=7 Hz, --CH₂ CH₃), 5.48 (2H, s, --CH₂ O--), 7.20-7.40 (m, 9H)

SYNTHESIS EXAMPLE 4 Synthesis of 1-ethyl-4-(2-chloro-4-methanesulfonylbenzoyl)-5-hydroxypyrazole

After 2.35 g (0.021 mol) of 1-ethyl-5-hydroxypyrazole was dissolved in 20 ml of tert.-amyl alcohole, the mixture was succesively added with 4.69 g (0.02 mol) of 2-chloro-4-methanesulfonyl benzoic acid, 5.33 g (0.021 mol) of N,N'-dicyclohexyl carbodiimide and 1.52 g (0.011 mol) of anhydrous potassium carbonate, and heated at 50°-60° C. for 5 hours, followed by additional stirring for 1 hour at 90° C. Then, the reaction was ceased. After cooling, solvent was distilled off from the reaction solution, and the residue was added with 50 ml of 5% aqueous solution of potassium hydroxide to dissolve the soluble matter. After insoluble matter was filtered off, the aqueous layer was washed with chloroform and separated. This operation was twice carried out. The obtained aqueous layer was adjusted to pH <1 by adding concentrated hydrochloric acid, and the precipitated solid product was dissolved in chloroform and extracted. After the chloroform layer was dried over sodium sulfate anhydrate, the solvent was distilled off to give a crude product of the objective product. Then, the crude product was recrystallized from 95% ethanol to obtain 5.38 g of 1-ethyl-4-(2-chloro-4-methanesulfonylbenzoyl)-5-hydroxypyrazole.

Yield: 82%

m.p.: 172.0°-175.0° C.

SYNTHESIS EXAMPLE 5 Synthesis of 1-ethyl-4-(2-chloro-3-methyl-4-methanesulfonylbenzoyl)-5-hydroxypyrazole

5.34 g of the objective 1-ethyl-4-(2-chloro-3-methyl-4-methanesulfonylbenzoyl)-5-hydroxypyrazole were obtained in the same operation and treatment as the Synthesis Examples 4 except that 4.69 g (0.02 mol) of 2-chloro-4-methanesulfonyl benzoic acid were replaced by 4.97 g (0.02 mol) of 2-chloro-3-methyl-4-methanesulfonyl benzoic acid.

Yield: 78%

m.p.: 225.0°-227.0° C.

SYNTHESIS EXAMPLE 6 Synthesis of 4-(2-chloro-4-methanesulfonyl)-1-ethyl-5-hydroxypyrazole

1.5 g (0.01 mol) of 1-ethyl-5-hydroxypyrazole hydrochloride was portionwise added to a solution of 1.3 g of potassium hydroxide (purity: 85%) in 10 ml of water with stirring under ice-cooling to give potassium salt thereof. Then, 10 ml of chloroform was added to the mixture to form two layers. To the two-layer mixture was portionwise added 2.5 g (0.01 mol) of 2-chloro-4-methanesulfonylbenzoyl chloride by keeping the temperature at below 5° C. The resulting mixture was stirred at the room temperature for 2 hours, followed by further stirring at 40° C. for 1 hour. After the reaction mixture was cooled, the chloroform layer was separated, and was successively washed with 5% aqueous solution of NaHCO₃, water, saturated brine. Then, the reaction mixture was dried over sodium sulfate anhydride and the solvent was distilled off under reduced pressure. The residue was dissolved in 2 ml of 1,4-dioxane and heated to 120° C. and then, was added with 2.1 g (0.015 mol) of anhydrous potassium carbonate at 120° C. and further heated for about 3 hours. After the temperature was left to cool to 90° C., the mixture was added water and dissolved, then the temperature was returned to the room temperature. After that, the mixture was adjusted to pH to <1 by adding hydrochloric acid. The precipitated solid matter was filtered, dried and recrystallized from ethanol to obtain 1.8 g of the title compound.

Yield: 55%

The compounds listed in Table 1 were synthesized in the same manner as Synthesis Example 1. However, the present invention is not limited to these compounds.

                  TABLE 1                                                          ______________________________________                                          ##STR11##                                                                     R         Yield (%) .sup.1 HNMR(δ, ppm) [solvent]                        ______________________________________                                         C.sub.2 H.sub.5                                                                          72                                                                                        ##STR12##                                                 C.sub.3 H.sub.7                                                                          66                                                                                        ##STR13##                                                 CH(CH.sub.3).sub.2                                                                       68                                                                                        ##STR14##                                                  ##STR15##                                                                               53        4.98(2H, s, NCH.sub.2), 5.43(1H, d, J=2Hz,                                     CCH.sub.2), 5.60(1H, d, J=2Hz CCH.sub.2), 5.94(1H, d,                          J=3Hz, CH), 7.73(1H, d, J=3Hz, CH) [CDCl.sub.3                                 +DMSOd.sub.6 ]                                             CH.sub.2 CHCH.sub.2                                                                      61        4.80(2H, d, J=5Hz, NCH.sub.2),                                                 5.06˜6.20(3H, m, CHCH.sub.2),                                            5.97(1H, d, J=3Hz, CH),                                                        7.85(1H, d, J=3Hz, CH)                                                         [CDCl.sub.3 +DMSOd.sub.6 ]                                 C(CH.sub.3).sub.3                                                                        46        1.68(9H, s, C(CH.sub.3).sub.3), 6.08(1H, d,                                    J=3.5Hz, CH), 7.79(1H, d,                                                      J=3.5Hz, CH), 10.65(2H, s)                                                     [CDCl.sub. 3 -DMSOd.sub.6 ]                                ______________________________________                                    

The compounds synthesized according to Synthesis Examples 2-5 are listed in Table 2.

                                      TABLE 2                                      __________________________________________________________________________      ##STR16##                                                                     Compound No.                                                                           R  Xn              Q     m.p. (°C.)                             __________________________________________________________________________     1       Et 2,4-Cl.sub.2    H     144-146                                       2       Et 2,4-Cl.sub.2    benzyl                                                                               oil (NMR-2)                                   3       Et 2,4-Cl.sub.2    tosyl oil (NMR-3)                                   4       Et 2,4-Cl.sub.2    phenacyl                                                                             97.5-99                                       5       Et 2,4-Cl.sub.2    mesyl                                               6       Et 2,4-Cl.sub.2    acetyl                                              7       Et 2,4-Cl.sub.2    α-methyl-                                                                      oil (NMR-7)                                                              benzyl                                              8       Et 2,4-Cl.sub.2    2-chloro-                                                                            oil (NMR-8)                                                              benzyl                                              9       Et 2,4-Cl.sub.2    4-nitro-                                                                             100-102                                                                  benzyl                                              10      Et 2,4-Cl.sub.2    2-methyl-                                                                            oil (NMR-10)                                                             benzyl                                              11      Et 2,4-Cl.sub.2    2-chloro-                                                                            oil (NMR-11)                                                             allyl                                               12      Et 2,4-Cl.sub.2    propar-                                                                              oil (NMR-12)                                                             gyl                                                 13      Et 2,4-Cl.sub.2    2,4-dichlo-                                                                          174.5-175                                                                robenzoyl                                           14      Et 2,4-Cl.sub.2    benzoyl                                             15      Et 2,4-Cl.sub.2    4-methyl-                                                                      phenacyl                                            16      Et 2,4-Cl.sub.2    α-methyl-                                                                phenacyl                                            17      Et 2,4-Cl.sub.2    2,4-dichlo-                                                                    benzyl                                              18      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        H     172-175                                       19      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        benzyl                                                                               126-129                                       20      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        tosyl 150-151                                       21      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        phenacyl                                                                             172-173                                       22      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        mesyl 204-206                                       23      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        acetyl                                              24      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        benzoyl                                             25      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        α-methyl-                                                                benzyl                                              26      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        2-methyl-                                                                      benzyl                                              27      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        2-chloro-                                                                      benzyl                                              28      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H     225-227                                       29      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                                                               oil (NMR-29)                                  30      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               31      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              phenacyl                                            32      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              mesyl                                               33      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              acetyl                                              34      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzoyl                                             35      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              α -methyl-                                                               benzyl                                              36      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              2-methyl-                                                                      benzyl                                              37      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              2-chloro-                                                                      benzyl                                              38      Et.                                                                               2,4-Cl.sub.23-CH.sub.3                                                                         H     126-127                                       39      Et.                                                                               2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                                                               oil (NMR-39)                                  40      Et.                                                                               2,4-Cl.sub.23-CH.sub.3                                                                         tosyl                                               41      Et.                                                                               2,4-Cl.sub.23-CH.sub.3                                                                         phenacyl                                                                             oil (NMR-41)                                  42      Et.                                                                               2,4-Cl.sub.23-CH.sub.3                                                                         2-chloro-                                                                            oil (NMR-42)                                                             benzyl                                              43      Et.                                                                               2-NO.sub.24-Cl  H     174-176                                       44      Et.                                                                               2-NO.sub.24-Cl  benzyl                                                                               oil (NMR-44)                                  45      Et.                                                                               2-NO.sub.24-Cl  tosyl oil (NMR-45)                                  46      Et.                                                                               2-NO.sub.24-Cl  phenacyl                                            47      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        allyl                                               48      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        propargyl                                           49      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              allyl                                               50      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              propargyl                                           51      Et.                                                                               2-Cl4-SO.sub.2 CH.sub.3                                                                        methyl                                              52      Et.                                                                               2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              methyl                                              53      Et.                                                                               2-Br4-SO.sub.2 CH.sub.3                                                                        H     157-163                                       54      Et.                                                                               2-Br4-SO.sub.2 CH.sub.3                                                                        benzyl                                              55      Et.                                                                               2-Br4-SO.sub.2 CH.sub.3                                                                        tosyl                                               56      Et.                                                                               2-Br4-SO.sub.2 CH.sub.3                                                                        phenacyl                                            57      Et.                                                                               2-Br4-SO.sub.2 CH.sub.3                                                                        mesyl                                               58      Et.                                                                               2-Br4-SO.sub.2 CH.sub.3                                                                        acetyl                                              59      Et.                                                                               2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   60      Et.                                                                               2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              61      Et.                                                                               2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               62      Et.                                                                               2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              phenacyl                                            63      Et.                                                                               2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              mesyl                                               64      Et.                                                                               2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              acetyl                                              65      Et.                                                                               2-F4-SO.sub.2 CH.sub.3                                                                         H                                                   66      Et.                                                                               2-F4-SO.sub.2 CH.sub.3                                                                         benzyl                                              67      Et.                                                                               2-F4-SO.sub.2 CH.sub.3                                                                         tosyl                                               68      Et.                                                                               2-F4-SO.sub.2 CH.sub.3                                                                         phenacy                                             69      Et.                                                                               2-F4-SO.sub.2 CH.sub.3                                                                         mesyl                                               70      Et.                                                                               2-F4-SO.sub.2 CH.sub.3                                                                         acetyl                                              71      Et.                                                                               2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   72      Et.                                                                               2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               benzyl                                              73      Et.                                                                               2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               tosyl                                               74      Et.                                                                               2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H     160-164                                       75      Et.                                                                               2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  benzyl                                              76      Et.                                                                               2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  tosyl                                               77      Et.                                                                               2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  phenacyl                                                                             154-157                                       78      Et.                                                                               2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  mesyl                                               79      Et.                                                                               2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  acetyl                                              80      Et.                                                                               2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H     202-203                                       81      Et.                                                                               2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        tosyl                                               82      Et.                                                                               2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        phenacyl                                            83      Et.                                                                               2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        mesyl                                               84      Et.                                                                               2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        acetyl                                              85      Et.                                                                               2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        benzyl                                                                               oil (NMR-85)                                  86      Et.                                                                               2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   87      Et.                                                                               2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                benzyl                                              88      Et.                                                                               2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                phenacyl                                            89      Et.                                                                               2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                tosyl                                               90      Et.                                                                               2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                mesyl                                               91      Et.                                                                               2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                acetyl                                              92      Et.                                                                               2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   93      Et.                                                                               2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    benzyl                                              94      Et.                                                                               2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    phenacyl                                            95      Et.                                                                               2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    tosyl                                               96      Et.                                                                               2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    mesyl                                               97      Et.                                                                               2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    acetyl                                              98      Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  H                                                   99      Et.                                                                               2,4-(SO.sub. 2 CH.sub.3).sub.2                                                                 benzyl                                              100     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  tosyl                                               101     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  mesyl                                               102     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  acetyl                                              103     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  phenacyl                                            104     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        H                                                   105     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        benzyl                                              106     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        tosyl                                               107     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        phenacyl                                            108     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        mesyl                                               109     Et.                                                                               2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        acetyl                                              110     Et.                                                                               2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   111     Et.                                                                               2-CN4-SO.sub.2 CH.sub.3                                                                        benzyl                                              112     Et.                                                                               2-CN4-SO.sub.2 CH.sub.3                                                                        tosyl                                               113     Et.                                                                               2-CN4-SO.sub.2 CH.sub.3                                                                        phenacyl                                            114     Et.                                                                               2-CN4-SO.sub.2 CH.sub.3                                                                        mesyl                                               115     Et.                                                                               2-CN4-SO.sub.2 CH.sub.3                                                                        acetyl                                              116     Et.                                                                               2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   117     Et.                                                                               2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              118     Et.                                                                               2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               119     Et.                                                                               2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   120     Et.                                                                               2-I4-SO.sub.2 CH.sub. 3                                                                        benzyl                                              121     Et.                                                                               2-I4-SO.sub.2 CH.sub.3                                                                         tosyl                                               122     Et.                                                                               2-I3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   123     Et.                                                                               2-I3-CH.sub.34-SO.sub.2 CH.sub.3                                                               benzyl                                              124     Et.                                                                               2-Cl4-SO.sub.2 Et                                                                              H                                                   125     Et.                                                                               2-Cl4-SO.sub.2 Et                                                                              benzyl                                              126     Et.                                                                               2-Cl4-SO.sub.2 Et                                                                              tosyl                                               127     Et.                                                                               2-Cl4-SO.sub.2.sup.i Pr                                                                        H     156-158                                       128     Et.                                                                               2-Cl4-SO.sub.2.sup.i Pr                                                                        benzyl                                                                                 104-105.5                                   129     Et.                                                                               2-Cl4-SO.sub.2.sup.i Pr                                                                        tosyl                                               130     Et.                                                                               2-Cl4-SO.sub.2.sup.n Pr                                                                        H     153-154                                       131     Et.                                                                               2-Cl4-SO.sub.2.sup.n Pr                                                                        benzyl                                                                               oil (NMR-131)                                 132     Et.                                                                               2-Cl4-SO.sub.2.sup.n Pr                                                                        tosyl 115-116                                       133     Et.                                                                               2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   134     Et.                                                                               2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  benzyl                                              135     Et.                                                                               2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  tosyl                                               136     Et.                                                                               2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  mesyl                                               137     Et.                                                                               2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  phenacyl                                            138     Et.                                                                               2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  acetyl                                              139     Et.                                                                               2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   140     Et.                                                                               2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  benzyl                                              141     Et.                                                                               2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  tosyl                                               142     Et.                                                                               2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   143     Et.                                                                               2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        benzyl                                              144     Et.                                                                               2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        tosyl                                               145     .sup.i Pr                                                                         2,4-Cl.sub.2    H     151-154                                       146     .sup.i Pr                                                                         2,4-Cl.sub.2    benzyl                                                                               oil (NMR-146)                                 147     .sup.i Pr                                                                         2,4-Cl.sub.2    phenacyl                                            148     .sup.i Pr                                                                         2,4-Cl.sub.2    tosyl                                               149     .sup.i Pr                                                                         2,4-Cl.sub.2    α-methyl                                                                 benzyl                                              150     .sup.i Pr                                                                         2,4-Cl.sub.2    2-chloro                                                                       benzyl                                              151     .sup.i Pr                                                                         2,4-Cl.sub.2    2-methyl                                                                       benzyl                                              152     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        H     181-184                                       153     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        benzyl                                                                               164-166                                       154     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        phenacyl                                            155     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        tosyl                                               156     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        mesyl                                               157     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        benzoyl                                             158     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        acetyl                                              159     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        propargyl                                           160     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        allyl                                               161     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        methyl                                              162     .sup.i Pr                                                                         2-Cl3-CH.sub. 34-SO.sub.2 CH.sub.3                                                             H       179-181.5                                   163     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              164     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              phenacyl                                            165     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               166     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              mesyl                                               167     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzoyl                                             168     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              acetyl                                              169     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              propargyl                                           170     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              allyl                                               171     .sup.i Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              methyl                                              172     .sup.i Pr                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         H                                                   173     .sup.i Pr                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                              174     .sup.i Pr                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         tosyl                                               175     .sup.i Pr                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         phenacyl                                            176     .sup.i Pr                                                                         2-NO.sub.24-Cl  H                                                   177     .sup.i Pr                                                                         2-NO.sub.24-Cl  benzyl                                              178     .sup.i Pr                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        H                                                   179     .sup.i Pr                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        benzyl                                              180     .sup.i Pr                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        tosyl                                               181     .sup.i Pr                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   182     .sup.i Pr                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              183     .sup.i Pr                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               184     .sup.i Pr                                                                         2-F4-SO.sub.2 CH.sub.3                                                                         H                                                   185     .sup.i Pr                                                                         2-F4-SO.sub.2 CH.sub.3                                                                         benzyl                                              186     .sup.i Pr                                                                         2-F4-SO.sub.2 CH.sub.3                                                                         tosyl                                               187     .sup.i Pr                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   188     .sup.i Pr                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               benzyl                                              189     .sup.i Pr                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               tosyl                                               190     .sup.i Pr                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   191     .sup.i Pr                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  benzyl                                              192     .sup.i Pr                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  tosyl                                               193     .sup.i Pr                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H     163-165                                       194     .sup.i Pr                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        benzyl                                                                               oil (NMR-194)                                 195     .sup.i Pr                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        tosyl                                               196     .sup.i Pr                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   197     .sup.i Pr                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                benzyl                                              198     .sup.i Pr                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                tosyl                                               199     .sup.i Pr                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   200     .sup.i Pr                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    benzyl                                              201     .sup.i Pr                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    tosyl                                               202     .sup.i Pr                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    mesyl                                               203     .sup.i Pr                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    acetyl                                              204     .sup.i Pr                                                                         2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  H                                                   205     .sup.i Pr                                                                         2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  benzyl                                              206     .sup.i Pr                                                                         2,4-(SO.sub.2 CH.sub.3).sub.2                                                                  tosyl                                               207     .sup.i Pr                                                                         2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        H                                                   208     .sup.i Pr                                                                         2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        benzyl                                              209     .sup.i Pr                                                                         2,4-(SO.sub.2 CH.sub.3).sub.23-CH.sub.3                                                        tosyl                                               210     .sup.i Pr                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   211     .sup.i Pr                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        benzyl                                              212     .sup.i Pr                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        tosyl                                               213     .sup.i Pr                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   214     .sup.i Pr                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              215     .sup.i Pr                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               216     .sup.i Pr                                                                         2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   217     .sup.i Pr                                                                         2-I4-SO.sub.2 CH.sub.3                                                                         benzyl                                              218     .sup.i Pr                                                                         2-Cl4-SO.sub.2 Et                                                                              H                                                   219     .sup.i Pr                                                                         2-Cl4-SO.sub.2 Et                                                                              benzyl                                              220     .sup.i Pr                                                                         2-Cl4-SO.sub.2.sup.i Pr                                                                        H     148-151                                       221     .sup.i Pr                                                                         2-Cl4-SO.sub.2.sup.i Pr                                                                        benzyl                                                                               oil (NMR-221)                                 222     .sup.i Pr                                                                         2-Cl4-SO.sub.2.sup.n Pr                                                                        H                                                   223     .sup.i Pr                                                                         2-Cl4-SO.sub.2.sup.n Pr                                                                        benzyl                                              224     .sup.i Pr                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   225     .sup.i Pr                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  benzyl                                              226     .sup.i Pr                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  tosyl                                               227     .sup.i Pr                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   228     .sup.i Pr                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        benzyl                                              229     .sup.i Pr                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        tosyl                                               230     .sup.i Pr                                                                         2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   231     allyl                                                                             2,4-Cl.sub.2    H                                                   232     allyl                                                                             2,4-Cl.sub.2    benzyl                                                                               oil (NMR-232)                                 233     allyl                                                                             2,4-Cl.sub.2    tosyl                                               234     allyl                                                                             2,4-Cl.sub.2    phenacyl                                            235     allyl                                                                             2-Cl4-SO.sub.2 CH.sub.3                                                                        H                                                   236     allyl                                                                             2-Cl 4-SO.sub.2 CH.sub.3                                                                       benzyl                                              237     allyl                                                                             2-Cl4-SO.sub.2 CH.sub.3                                                                        tosyl                                               238     allyl                                                                             2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   239     allyl                                                                             2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              240     allyl                                                                             2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              tosyl                                               241     allyl                                                                             2,4-Cl.sub.23-CH.sub.3                                                                         H                                                   242     allyl                                                                             2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                              243     allyl                                                                             2-NO.sub.24-Cl  H                                                   244     allyl                                                                             2-Br4-SO.sub.2 CH.sub.3                                                                        H                                                   245     allyl                                                                             2-Br4-SO.sub.2 CH.sub.3                                                                        benzyl                                              246     allyl                                                                             2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   247     allyl                                                                             2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              248     allyl                                                                             2-F4-SO.sub.2 CH.sub.3                                                                         H                                                   249     allyl                                                                             2-F4-SO.sub.2 CH.sub.3                                                                         benzyl                                              250     allyl                                                                             2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   251     allyl                                                                             2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   252     allyl                                                                             2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  benzyl                                              253     allyl                                                                             2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   254     allyl                                                                             2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    benzyl                                              255     allyl                                                                             2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H                                                   256     allyl                                                                             2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   257     allyl                                                                             2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   258     allyl                                                                             2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   259     allyl                                                                             2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   260     allyl                                                                             2-I3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   261     allyl                                                                             2-Cl4-SO.sub.2 Et                                                                              H                                                   262     allyl                                                                             2-Cl4-SO.sub.2.sup.i Pr                                                                        H                                                   263     allyl                                                                             2-Cl4-SO.sub.2.sup.n Pr                                                                        H                                                   264     allyl                                                                             2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   265     allyl                                                                             2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  benzyl                                              266     allyl                                                                             2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   266     allyl                                                                             2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        benzyl                                              267     allyl                                                                             2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   268     .sup.n Pr                                                                         2,4-Cl.sub.2    H     oil (NMR-268)                                 269     .sup.n Pr                                                                         2,4-Cl.sub.2    benzyl                                                                               oil (NMR-269)                                 270     .sup.n Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        H                                                   271     .sup.n Pr                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        benzyl                                              272     .sup.n Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   273     .sup.n Pr                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              274     .sup.n Pr                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         H                                                   275     .sup.n Pr                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                              276     .sup.n Pr                                                                         2-NO.sub.24-Cl  H                                                   277     .sup.n Pr                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        H                                                   278     .sup.n Pr                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   279     .sup. n Pr                                                                        2-F4-SO.sub.2 CH.sub.3                                                                         H                                                   280     .sup.n Pr                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   281     .sup.n Pr                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   282     .sup.n Pr                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   283     .sup.n Pr                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H                                                   284     .sup.n Pr                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   285     .sup.n Pr                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   286     .sup.n Pr                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   287     .sup.n Pr                                                                         2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   288     .sup.n Pr                                                                         2-I3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   289     .sup.n Pr                                                                         2-Cl4-SO.sub.2 Et                                                                              H                                                   290     .sup.n Pr                                                                         2-Cl4-SO.sub.2.sup.i Pr                                                                        H                                                   291     .sup.n Pr                                                                         2-Cl4-SO.sub.2.sup.n Pr                                                                        H                                                   292     .sup.n Pr                                                                         2,4-Cl.sub.2    4-ethyl                                                                              oil (NMR-292)                                                            benzyl                                              293     .sup.n Pr                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   294     .sup.n Pr                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   295     .sup.n Pr                                                                         2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   296     .sup.n Bu                                                                         2,4-Cl.sub.2    H     oil (NMR-296)                                 297     .sup.n Bu                                                                         2,4-Cl.sub.2    benzyl                                                                               oil (NMR-297)                                 298     .sup.n Bu                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        H                                                   299     .sup.n Bu                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        benzyl                                              300     .sup.n Bu                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   301     .sup.n Bu                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              302     .sup.n Bu                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         H                                                   303     .sup.n Bu                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                              304     .sup.n Bu                                                                         2-NO.sub.24-Cl  H                                                   305     .sup.n Bu                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        H                                                   306     .sup.n Bu                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   307     .sup.n Bu                                                                         2-F4-SO.sub.2 CH.sub.3                                                                         H                                                   308     .sup.n Bu                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   309     .sup.n Bu                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   310     .sup.n Bu                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   311     .sup.n Bu                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H                                                   312     .sup.n Bu                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   313     .sup.n Bu                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   314     .sup.n Bu                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   315     .sup.n Bu                                                                         2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   316     .sup.n Bu                                                                         2-I3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   317     .sup.n Bu                                                                         2-Cl4-SO.sub.2 Et                                                                              H                                                   318     .sup.n Bu                                                                         2-Cl4-SO.sub.2.sup.i Pr                                                                        H                                                   319     .sup.n Bu                                                                         2-Cl4-SO.sub.2.sup.n Pr                                                                        H                                                   320     .sup.n Bu                                                                         2,4-Cl.sub.2    2-chloro-                                                                            oil (NMR-320)                                                            benzyl                                              321     .sup.n Bu                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   322     .sup.n Bu                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   323     .sup.n Bu                                                                         2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   324     .sup.i Bu                                                                         2,4-Cl.sub.2    H                                                   325     .sup.i Bu                                                                         2,4-Cl.sub.2    benzyl                                              326     .sup.i Bu                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        H                                                   327     .sup.i Bu                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        benzyl                                              328     .sup.i Bu                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   329     .sup.i Bu                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              330     .sup.i Bu                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         H                                                   331     .sup.i Bu                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                              332     .sup.i Bu                                                                         2-NO.sub.24-Cl  H                                                   333     .sup.i Bu                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        H                                                   334     .sup.i Bu                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   335     .sup.i Bu                                                                         2-F4-SO.sub.2 CH.sub. 3                                                                        H                                                   336     .sup.i Bu                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   337     .sup.i Bu                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   338     .sup.i Bu                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   339     .sup.i Bu                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H                                                   340     .sup.i Bu                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   341     .sup.i Bu                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   342     .sup.i Bu                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   343     .sup.i Bu                                                                         2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   344     .sup.i Bu                                                                         2-I3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   345     .sup.i Bu                                                                         2-Cl4-SO.sub.2 Et                                                                              H                                                   346     .sup.i Bu                                                                         2-Cl4-SO.sub.2.sup.i Pr                                                                        H                                                   347     .sup.i Bu                                                                         2-Cl4-SO.sub.2.sup.n Pr                                                                        H                                                   348     .sup.i Bu                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   349     .sup.i Bu                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   350     .sup.i Bu                                                                         2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   351     .sup.s Bu                                                                         2,4-Cl.sub.2    H     86-88                                         352     .sup.s Bu                                                                         2,4-Cl.sub.2    benzyl                                                                               oil (NMR-352)                                 353     .sup.s Bu                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        H                                                   354     .sup.s Bu                                                                         2-Cl4-SO.sub.2 CH.sub.3                                                                        benzyl                                              355     .sup.s Bu                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   356     .sup.s Bu                                                                         2-Cl3-CH.sub.34-SO.sub.2 CH.sub.3                                                              benzyl                                              357     .sup.s Bu                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         H                                                   358     .sup.s Bu                                                                         2,4-Cl.sub.23-CH.sub.3                                                                         benzyl                                              359     .sup.s Bu                                                                         2-NO.sub.24-Cl  H                                                   360     .sup.s Bu                                                                         2-Br4-SO.sub.2 CH.sub.3                                                                        H                                                   361     .sup.s Bu                                                                         2-Br3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   362     .sup.s Bu                                                                         2-F4-SO.sub.2 CH.sub.3                                                                         H                                                   363     .sup.s Bu                                                                         2-F3-CH.sub.34-SO.sub.2 CH.sub.3                                                               H                                                   364     .sup.s Bu                                                                         2-CH.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   365     .sup.s Bu                                                                         2-Cl3-Et4-SO.sub.2 CH.sub.3                                                                    H                                                   366     .sup.s Bu                                                                         2,3-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                        H                                                   367     .sup.s Bu                                                                         2,3-Cl.sub.24-SO.sub.2 CH.sub.3                                                                H                                                   368     .sup.s Bu                                                                         2-CN4-SO.sub.2 CH.sub.3                                                                        H                                                   369     .sup.s Bu                                                                         2-CN3-CH.sub.34-SO.sub.2 CH.sub.3                                                              H                                                   370     .sup.s Bu                                                                         2-I4-SO.sub.2 CH.sub.3                                                                         H                                                   371     .sup.s Bu                                                                         2-I3-CH.sub.34-SO.sup.2 CH.sub.3                                                               H                                                   372     .sup.s Bu                                                                         2-Cl4-SO.sub.2 Et                                                                              H                                                   373     .sup.s Bu                                                                         2-Cl4-SO.sub.2.sup.i Pr                                                                        H                                                   374     .sup.s Bu                                                                         2-Cl4-SO.sub.2.sup.n Pr                                                                        H                                                   375     .sup.s Bu                                                                         2,4-Cl.sub.2    2,4-chloro-                                                                            139-141.5                                                              benzoyl                                             376     .sup.s Bu                                                                         2-NO.sub.24-SO.sub.2 CH.sub.3                                                                  H                                                   377     .sup.s Bu                                                                         2-NO.sub.23-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   378     .sup.s Bu                                                                         2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   379     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   380     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  benzyl                                              381     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  tosyl                                               382     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  phenacyl                                            383     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  mesyl                                               384     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  benzoyl                                             385     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  allyl                                               386     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  propargyl                                           387     Et 2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  methyl                                              388     Et 2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   389     Et 2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        benzyl                                              390     Et 2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        tesyl                                               391     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   392     .sup.i Pr                                                                         2-CF.sub.3 4-SO.sub.2 CH.sub.3                                                                 benzyl                                              393     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  tosyl                                               394     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  phenacyl                                            395     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  mesyl                                               396     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  benzoyl                                             397     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  allyl                                               398     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  propargyl                                           399     .sup.i Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  methyl                                              400     .sup.i Pr                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   401     .sup.i Pr                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        benzyl                                              402     .sup.i Pr                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        tesyl                                               403     .sup.n Pr                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   404     .sup.n Pr                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   405     .sup.n Bu                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   406     .sup.n Bu                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   407     .sup.i Bu                                                                         2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   408     .sup.i Bu                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   409     .sup.s Bu                                                                         2-CF.sub.34-SO.sub. 2 CH.sub.3                                                                 H                                                   410     .sup.s Bu                                                                         2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   411     allyl                                                                             2-CF.sub.34-SO.sub.2 CH.sub.3                                                                  H                                                   412     allyl                                                                             2-CF.sub.33-CH.sub.34-SO.sub.2 CH.sub.3                                                        H                                                   413     Et 2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   414     .sup.i Pr                                                                         2-SO.sub.2 CH.sub.35-CH.sub.3                                                                  H                                                   415     Et 2-Cl4-SO.sub.2 CH.sub.35-CH.sub.3                                                              H     142-144                                       416     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.35-CH.sub.3                                                              H     180-182                                       417     Et 2-NO.sub.24-SO.sub.2 CH.sub.35-CH.sub.3                                                        H                                                   418     .sup.i Pr                                                                         2-NO.sub.24-SO.sub.2 CH.sub.35-CH.sub.3                                                        H                                                   419     Et 2-Cl3,5-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                    H                                                   420     .sup.i Pr                                                                         2-Cl3,5-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                                    H                                                   421     Et 2-NO.sub.23,5-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                              H                                                   422     .sup.i Pr                                                                         2-NO.sub.23,5-(CH.sub.3).sub.24-SO.sub.2 CH.sub.3                                              H                                                   423     Et 2-CH.sub.34-Cl  H                                                   424     Et 2-CH.sub.34-Cl  benzyl                                              425     Et 2-CH.sub.34-Cl  tosyl                                               426     Et 2-CH.sub.34-Cl  phenacyl                                            427     .sup.i Pr                                                                         2-CH.sub.34-Cl  H                                                   428     .sup.i Pr                                                                         2-CH.sub.34-Cl  benzyl                                              429     .sup.i Pr                                                                         2-CH.sub.34-Cl  tosyl                                               430     .sup.i Pr                                                                         2-CH.sub.34-Cl  phenacyl                                            431     Et 2,3-(CH.sub.3).sub.24-Cl                                                                       H                                                   432     Et 2,3-(CH.sub.3).sub.24-Cl                                                                       benzyl                                              433     .sup.i Pr                                                                         2,3-(CH.sub.3).sub.24-Cl                                                                       H                                                   434     .sup.i Pr                                                                         2,3-(CH.sub.3).sub.24-Cl                                                                       benzyl                                              435     Et 2-Cl4-SO.sub.2 CH.sub.35-CH.sub.3                                                              benzyl                                                                               105-106                                       436     .sup.i Pr                                                                         2-Cl4-SO.sub.2 CH.sub.35-CH.sub.3                                                              benzyl                                              437     Et 2-CH.sub.33-Cl4-SO.sub.2 CH.sub.3                                                              H                                                   438     Et 2-CH.sub.33-Cl4-SO.sub.2 CH.sub.3                                                              benzyl                                              439     .sup.i Pr                                                                         2-CH.sub.33-Cl4-SO.sub.2 CH.sub.3                                                              H                                                   440     .sup.i Pr                                                                         2-CH.sub.33-Cl4-SO.sub.2 CH.sub.3                                                              benzyl                                              441     Et 2-CH.sub.33,4-Cl.sub.2                                                                         H                                                   442     Et 2-CH.sub.33,4-Cl.sub.2                                                                         benzyl                                              443     .sup.i Pr                                                                         2-CH.sub.33,4-Cl.sub.2                                                                         H                                                   444     .sup.i Pr                                                                         2-CH.sub.33,4-Cl.sub.2                                                                         benzyl                                              445     Et 2-CH.sub.33-Br4-SO.sub.2 CH.sub.3                                                              H                                                   446     .sup.i Pr                                                                         2-CH.sub.33-Br4-SO.sub.2 CH.sub.3                                                              H                                                   __________________________________________________________________________      (Note)                                                                         Et = CH.sub.3 CH.sub.2,                                                        .sup.n Bu = CH.sub.3 (CH.sub.2).sub.3,                                         allyl = CH.sub.2CHCH.sub.2-                                                    .sup.n Pr = CH.sub.3 CH.sub.2 CH.sub.2,                                        .sup.i Bu = (CH.sub.3).sub.2 CHCH.sub.2                                        .sup.i Pr = (CH.sub.3).sub.2 CH,                                               ##STR17##                                                                

    ______________________________________                                         .sup.1 HNMR                                                                            δ (ppm) [solvent]                                                ______________________________________                                         NMR-2   1.19 (3H, t, CH.sub.3), 3.83 (2H, q,  ---CH.sub.2 CH.sub.3),                   5.48 (2H, s, o --CH.sub.2), 7.20-7.40 (9H, m)                                  [CDCl.sub.3 ]                                                          NMR-3   4.14 (2H, q,  ---CH.sub.2 CH.sub.3), 1.48 (3H, t,  ---CH.sub.2                 CH.sub.3),                                                                     2.43 (3H, s, CH.sub.3)                                                         [CDCl.sub.3 ]                                                          NMR-7   6.11 (1H, q, CH), 3.80 (2H, q,  ---CH.sub.2 CH.sub.3),                         1.74 (3H, d, OCHC .sub.--H.sub.3), 1.15 (3H, t, CH.sub.2 C                     .sub.--.sub.3),                                                                7.17-7.42 (9H, m)                                                              [CDCl.sub.3 ]                                                          NMR-8   1.27 (3H, t, CH.sub.3), 3.94 (2H, q, C .sub.--H.sub.2 CH.sub.3),               5.62 (2H, s, O--CH.sub.2), 7.1-7.6 (8H, m)                                     [CDCl.sub.3 ]                                                          NMR-10  1.17 (3H, t, CH.sub.3), 2.41 (3H, s, CH.sub.3)                                 3.81 (2H, q, C .sub.--H.sub.2 CH.sub.3), 5.53 (2H, s,                          --OCH.sub.2)                                                                   7.0-7.5 (8H, m)                                                                [CDCl.sub.3 ]                                                          NMR-11  1.41 (3H, t, CH.sub.2 C .sub.--H.sub.3), 4.10 (2H, q,                          C .sub.--H.sub.2 CH.sub.3),                                                    5.18 (2H, s, --OCH.sub.2), 5.13 (1H, = CH.sub.2),                              5.51 (1H, = CH.sub.2), 7.2-7.5 (4H, m)                                         [CDCl.sub.3 ]                                                          NMR-12  1.44 (3H, t, CH.sub.2 CH.sub.3), 2.54 (1H, t, J=2 Hz, .tbd.CH)                 4.14 (2H, q, C .sub.--H.sub.2 CH.sub.3), 5.15 (2H, d, J=2 Hz,                  --C .sub.--H.sub.2 C.tbd.CH), 7.2-7.5 (4H, m)                                  [CDCl.sub.3 ]                                                          NMR-29  1.20 (3H, t, J=7 Hz, CH.sub.2 C .sub.--H.sub.3), 2.77 (3H, S,                  CH.sub.3),                                                                     3.08 (3H, s, SO.sub.2 CH.sub.3), 3.85 (2H, q, J=7 Hz,                          C .sub.--H.sub.2 CH.sub.3), 5.52 (2H, s, --O--CH.sub.2 --),                    7.15-7.35                                                                      (7H, m), 8.00 (1H, d)                                                          [CDCl.sub.3 ]                                                          NMR-39  1.19 (3H, t, CH.sub.2 C .sub.--H.sub.3), 2.47 3H, s, CH.sub.3),                3.83 (2H, q, C .sub.--H.sub.2 CH.sub.3), 5.51 (2H, s,                          OCH.sub.2),                                                                    7.00-7.38 (8H, m)                                                              [CDCl.sub.3 ]                                                          NMR-41  1.48 (3H, t, CH.sub.2 C .sub.--H.sub.3), 2.42 (3H, s, CH.sub.3),               4.22 (2H, q, C .sub.--H.sub.2 CH.sub.3), 6.07 (2H, s,                          OCH.sub.2),                                                                    6.91-7.88 (8H, m)                                                              [CDCl.sub.3 ]                                                          NMR-42  1.23 (3H, t, CH.sub.2 C .sub.--H.sub.3), 2.47 (3H, s, CH.sub.3),               3.92 (2H, q, C .sub.--H.sub.2 CH.sub.3), 5.62 (2H, s,                          OCH.sub.2),                                                                    7.01-7.50 (7H, m)                                                      NMR-44  1.14 (3H, t, CH.sub.2 C .sub.--H.sub.3), 3.79 (2H, q,                          C .sub.--H.sub.2 CH.sub.3),                                                    5.45 (2H, s, OCH.sub.2), 7.22-8.01 (9H, m)                                     [CDCl.sub.3 ]                                                          NMR-45  1.46 (3H, t, CH.sub.2 C .sub.--H.sub.3), 2.43 (3H, s)                          4.10 (2H, q, C .sub.--H.sub.2 CH.sub.3), 7.28-7.98 (8H, m)                     [CDCl.sub.3 ]                                                          NMR-85  1.22 (3H, t, J=7 Hz, CH.sub.2 C .sub.--H.sub.3), 2.29 (3H, s,                  CH.sub.3),                                                                     2.66 (3H, s, CH.sub.3), 3.08 (3H, s, SO.sub.2 CH.sub.3),                       3.89 (2H, q, J=7 Hz, C .sub.--H.sub.2 CH.sub.3), 5.53 (2H,                     s, --CH.sub.2 O--) 7.20 (1H, s), 7.25-7.40 (6H, m),                            7.98 (1H, d)                                                                   [CDCl.sub.3 ]                                                          NMR-131 1.00 (3H, t, J=7 Hz, CH.sub.2 C .sub.--H.sub.3), 1.20 (3H, t, J=               7Hz, CH.sub.2 C .sub.--H.sub.3), 1.45-2.08 (2H, m, CH.sub.2 C                  .sub.--H.sub.2 CH.sub.3),                                                      2.94-3.20 (2H, m, --SO.sub.2 CH.sub.2 --), 3.85 (2H, q, J=7 Hz,                C .sub.--H.sub.2 CH.sub.3), 5.51 (2H, s, OCH.sub.2), 7.15-7.93                 (9H, m)                                                                        [CDCl.sub.3 ]                                                          NMR-146 1.21 (6H, d, CH(C .sub.--H.sub.3).sub.2), 4.43 (1H, q, q,                      C .sub.--H (CH.sub.3).sub.2), 5.50 (2H, s, OCH.sub.2)                          7.27-7.47 (9H, m)                                                              [CDCl.sub.3 ]                                                          NMR-194 1.26 (6H, d, J=7 Hz, CH(C .sub.--H.sub.3).sub.2), 2.31 (3H, s,                 CH.sub.3),                                                                     2.68 (3H, s, CH.sub.3), 3.09 (3H, s, SO.sub.2 CH.sub.3), 4.48                  (1H,                                                                           q-q, J=7 Hz, C .sub.--H(CH.sub.3).sub.2), 5.53 (2H, s,                         --O--CH.sub.2 --),                                                             7.22 (1H, s), 7.25-7.43 (6H, m), 8.01 (1H, d)                                  [CDCl.sub.3 ]                                                          NMR-221 1.23 (6H, d, J=7 Hz, CH(C .sub.--H.sub.3).sub.2), 1.33 (6H, d,                 J=7 Hz, CH(C .sub.--H.sub.3).sub.2), 3.22 (1H, q-q, J=7 Hz,                    C .sub.--H(CH.sub.3).sub.2), 4.43 (1H, q-q, J=7 Hz,                            C .sub.--H(CH.sub.3).sub.2),                                                   5.50 (2H, S, O--CH.sub.2), 7.19-7.93 (9H, m)                                   [CDCl.sub.3 ]                                                          NMR-232 4.45 (2H, d, C .sub.--H.sub.2 CH═CH.sub.2)                                 5.50 (2H, s, OCH.sub.2)                                                        [CDCl.sub.3 ]                                                          NMR-268 0.94 (3H, t, CH.sub.2 CH.sub.2 C .sub.--H.sub.3), 1.87 (2H,                    CH.sub.2 C .sub.--H.sub.2 CH.sub.3),                                           3.97 (2H, t, C .sub.--H.sub.2 CH.sub.2 CH.sub.3)                               7.13-7.50 (4H, m)                                                              [CDCl.sub.3 ]                                                          NMR-269 0.79 (3H, t, CH.sub.2 CH.sub.2 C .sub.--H.sub.3), 1.65 (2H,                    CH.sub.2 C .sub.--H.sub.2 CH.sub.3),                                           3.76 (2H, t, C .sub.--H.sub.2 CH.sub.2 CH.sub.3), 5.49 (2H, s,                 OCH.sub.2),                                                                    7.23-7.42 (9H, m)                                                              [CDCl.sub.3 ]                                                          NMR-292 0.81 (3H, t, CH.sub.3 ), 1.24 (3H, t, CH.sub.3), 1.66 (2H,                     CH.sub.2                                                                       C .sub.--H.sub.2 CH.sub.3), 2.64 (2H, q, C .sub.--H.sub.2                      CH.sub.3), 3.77 (2H, t, C .sub.--H.sub.2                                       CH.sub.2 CH.sub.3), 5.47 (2H, s, OCH.sub.2), 7.0-7.6 (8H, m)                   [CDCl.sub.3 ]                                                          NMR-296 0.95 (3H, t, CH.sub.3), 1.19-2.03 (4H, m), 3.99 (2H, t,                        C .sub.--H.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), 7.15-7.50 (4H, m),               10.8 (1H, s,                                                                   OH) [CDCl.sub.3 ]                                                      NMR-297 0.84 (3H, t, CH.sub.3), 1.03-1.71 (4H, m),                                     3.79 (2H, t, C .sub.--H.sub.2 CH.sub.2 CH.sub.2 CH.sub.3)                      7.25-7.45 (9H, m)                                                              [CDCl.sub.3 ]                                                          NMR-320 0.85 (3H, t, CH.sub.3), 1.06-1.80 (4H, m)                                      3.88 (2H, t, C .sub.--H.sub.2 CH.sub.2 CH.sub.2 CH.sub.3)                      7.15-7.46 (8H, m)                                                              [CDCl.sub.3 ]                                                          NMR-352 0.67 (3H, t, CH.sub.3 CHCH.sub.2 C  .sub.--H.sub.3), 1.18 (3H, d,              C .sub.--H.sub.3                                                               CHCH.sub.2 CH.sub.3), 1.62 (2H, m, CH.sub.3 CHC .sub.--H.sub.2                 CH.sub.3),                                                                     4.17 (1H, t, q, CH.sub.3 C .sub.--HCH.sub.2 CH.sub.3)                          5.50 (2H, s, OCH.sub.2), 7.1-7.7 (9H, m)                                       [CDCl.sub.3 ]                                                          ______________________________________                                    

When the compounds according to the present invention are used for a herbicide, they may be applied generally together with suitable carriers such as solid carriers, e.g., clay, talc, bentonite, diatomaceous earth, etc., or liquid carriers, e.g., water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.). It is possible to add, as necessary, surfactants, dispersing agents, suspending agents, penetrating agents, spreaders, stabilizers, etc. to form arbitrary formulations such as emulsifiable concentrate, wettable powder, flowable (Suspension Concentrate), granule, etc. for practical use.

If necessary, the compounds according to the invention may be mixed, during formulation or application, with other herbicides, various insecticides, bacteriocides, plant growth-regulator, cooper-ants, etc.

The other herbicides include the compounds described in "Farm Chemicals Handbook" 69th year of publication (1983).

In the following formulation examples, parts are by weight unless otherwise specified.

Formulation Example 1: Emulsifiable concentrate

    ______________________________________                                         Compound No. 19 of the present invention                                                                 30    parts                                          xylene                    45    parts                                          Sorpol 2680 ®         10    parts                                          (a mixture of non-ionic surfactant                                             and anionic surfactant; trade name                                             supplied by Toho Chemical Co., Ltd.,                                           Japan)                                                                         dimethylformamide         15    parts                                          ______________________________________                                    

The above ingredients are homogeneously blended with one another in suitable device to give an emulsifiable concentrate. When in use, it is diluted with a suitable amount of water and applied.

Formulation Example 2: Emulsifiable concentrate

    ______________________________________                                         Compound No. 77 of the invention                                                                        20    parts                                           xy1ene                   75    parts                                           Sorpol 2680 ®        5     parts                                           (a mixture of non-ionic surfactant                                             and anionic surfactant; trade name                                             supplied by Toho Chemical Co., Ltd.,                                           Japan)                                                                         ______________________________________                                    

The above ingredients are homogeneously blended with one another in suitable device to give an emulsifiable concentrate. When in use, it is diluted with a suitable amount of water and applied.

Formulation Example 3: Wettable powder

    ______________________________________                                         Compound No. 152 of the invention                                                                       50    parts                                           Zeeklite A ®         46    parts                                           (kaolin type clay: trade name                                                  supplied by Ziecleid Industries                                                Co., Ltd., Japan)                                                              Sorpol 5039 ®        2     parts                                           (a mixture of non-ionic surfactant                                             and anionic surfactant: trade name                                             supplied by Toho Chemical Co., Ltd.                                            Japan)                                                                         Carplex ® (coagulation inhibitor)                                                                   2     parts                                           (white carbon: trade name supplied                                             by Shionogi Pharmaceutical Co.,                                                Ltd., Japan)                                                                   ______________________________________                                    

The above ingredients are intimately mixed and ground in appropriate mills and rollers to give wettable powder. When in use, this wettable powder can be diluted with an appropriate amount of water to obtain suspensions of the concentration required and applied.

Formulation Example 4: Wettable powder

    ______________________________________                                         Compound 28 of the invention                                                                            50    parts                                           Zeeklite A ®         46    parts                                           (kaolin type clay: trade name                                                  supplied by Ziecleid Industries                                                Co., Ltd., Japan)                                                              Sorpol 5039 ®        2     parts                                           (a mixture of non-ionic surfactant                                             and anionic surfactant: trade name                                             supplied by Toho Chemical Co.,                                                 Ltd., Japan)                                                                   Carplex  ® (coagulation inhibitor)                                                                  2     parts                                           (white carbon: trade name supplied                                             by Shionogi Pharmaceutical Co.,                                                Ltd., Japan)                                                                   ______________________________________                                    

The above ingredients are intimately mixed and ground to give wettable powder. When in use, this wettable powder is diluted with an appropriate amount of water and applied.

Formulation Example 5: Flowable (Suspension Concentrate)

    ______________________________________                                         Compound No. 18 of the invention                                                                       25     parts                                           Agrisol 8-710 ®     10     parts                                           (non-ionic surfactant: trade name                                              supplied by Kao Atlas Co., ltd.                                                Japan)                                                                         Lunox 1000C ®       0.5    part                                            (anionic surfactant: trade name                                                supplied by Toho Chemical Co.,                                                 Ltd., Japan)                                                                   1% aqueous Rhodopol ®                                                                              20     parts                                           (thickening agent: trade name                                                  supplied by Rhone-Poulenc S.A.                                                 Water                   44.5   parts                                           ______________________________________                                    

The above ingredients are homogeneously mixed to give flowable. When in use, this flowable is diluted with an appropriate amount of water and applied.

Formulation Example 6: Flowable (Suspension Concentrate)

    ______________________________________                                         Compound No. 80 of the invention                                                                       25     parts                                           Agrisol 8-710 ®     10     parts                                           (non-ionic surfactant: trade name                                              supplied by Kao Atlas Co., Ltd.,                                               Japan)                                                                         Lunox 1000C ®       0.5    part                                            (anionic surfactant: trade name                                                supplied by Toho Chemical Co.,                                                 Ltd., Japan)                                                                   1% aqueous Rhodopol ®                                                                              20     parts                                           (thickening agent: trade name                                                  supplied by Rhone-Poulenc S.A.)                                                Water                   44.5   parts                                           ______________________________________                                    

The above ingredients are homogenously mixed to give flowable. When in use, this flowable is diluted with an appropriate amount of water and applied.

Formulation Example 7: Granule

    ______________________________________                                         Compound No. 2 of the invention                                                                         5     parts                                           bentonite                55    parts                                           talc                     40    parts                                           ______________________________________                                    

After the above ingredients are intimately mixed and ground, a small amount of water is added thereto and the mixture is kneaded well, granulated by means of an extrusion type granulator and dried to give granules.

The herbicidal compositions containing the compounds according to the present invention are applicable to non-cultivation lands such as athletic fields, vacant lands, railroad sides to damage and control a variety of weeds in addition to agricultural and horticultural lands such as farmlands, paddy fields, fruit gardens, etc. The application dosage of the compounds according to the invention may vary depending upon the place to be applied, application season, application manner, kind of weeds to be controlled, cultivated crops, etc., and is generally in the range of 0.01 to 10 kg per hectare (ha).

The herbicidal effectiveness of the compounds according to the present invention will be explained specifically by way of the following test examples.

BIOLOGICAL EXAMPLES Test Example 1: Herbicidal effect test in submerged conditions

After a certain amount of alluvial soil was placed in a Wagner pot of 1/5,000 are (a), water was added thereto to obtain a sub-merged state of 2 cm in water depth through well mixing. Then, seeds of rice (Oryza sativa) and Barnyard grass (Echinochloa crus-galli), braodleaf-weeds such as Monochoria vaginalis, Lindernia pyxidaria, Rotala indica, etc. and Scirpus juncoides were mixedly sowed in the submerged soil in the Wagner pot, and tubers of Sagittaria pygmaea, Cyperus serotinus and Eleocharis kuroguwai were placed therein. The pot was placed in the hothouse which keeps the temperature from 20°-25° C. to grow the plants.

On the 10th day after sowing, which corresponds to a period when rice and weeds were grown at 1-2 leaf stage, diluted solution of the chemical which was prepared to become predetermined amount of the chemical was added dropwise by means of a measuring pipette to the soil.

Three weeks after the addition of the chemical liquid, herbicidal effects to rice and each weed were evaluated in the following standard of judgement:

Evaluation Standard:

5-herbicidal rate above 90% (completely withered)

4-herbicidal rate 70-90%

3-herbicidal rate 40-70%

2-herbicidal rate 20-40%

1-herbicidal rate 5-20%

0-herbicidal rate below 5% (practically no efficacy).

The above herbicidal rate was calculated by the following equation based on the weight measured of live plants above soil in the herbicidal-treatment plot and the untreated plot. ##EQU1## wherein B: weight of live plant above soil in herbicide-treated plot and A: weight of live plant above soil in herbicide-untreated plot.

The results are shown in Table 3.

Test Example 2: Herbicidal effect by soil-treatment

Sterilized diluvial soil was placed in a plastic pot of 1/10000 are (a) in opening area and 10 cm in depth. Then were sown in spot-like corn (Zea mays), barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria viridis), crabgrass (Digitaria ciliaris), cocklebur, (Xanthium strumarium), velvet leaf (Abutilon theophrasti), smartweed (Polygonum nodosum), pigweed (Amaranthus ascendes) and yellow nutsedge (Cyperus esculentus), respectively. After the seeds were covered with the soil about 1.5 cm in depth, a diluted solution containing a predetermined amount of an active ingredient was applied uniformly over the surface of the soil.

The diluted solution was prepared by diluting with water the wettable powder or emulsifiable concentrate in the above formulation examples and applied by means of a small spray over the whole surface of the soil. Four weeks after the application, herbicidal effect against various weeds was evaluated according to the following evaluation rating. The results are shown in Table 4.

Evaluation rating:

5 . . . above 90% in herbicidal rate (completely withered)

4 . . . 70 to 90% in herbicidal rate

3 . . . 40 to 70% in herbicidal rate

2 . . . 20 to 40% in herbicidal rate

1 . . . 5 to 20% in herbicidal rate

0 . . . less than 5% in herbicidal rate (practically no effective).

The above herbicidal rate was calculated in similar manner with the Test Example 1.

Test Example 3: Phytotoxity test against cultivated plants by foliage-treatment

In a plastic box of 15 cm (length)×22 cm (width)×6 cm (depth) was placed sterilized diluvial soil, and corn was sown. After covering the seeds with the soil about 1.5 cm in depth and corn plant were grown until 2 leaf stage. A diluted solution containing a predetermined amount of an active ingredient was uniformly applied over the top of corn plant. The diluted solution was prepared by diluting with water the wettable powder or emulsifiable concentrate in the above formulation examples, and the resulting diluted solution was applied by means of a small spray over the whole surface of the plant. Three weeks after the application, phytotoxity against the above crops was evaluated according to the following evaluation rating. The results are shown in Table 5.

Evaluation rating:

5 . . . crops are almost completely withered.

4 . . . remarkable phytotoxity against crops is observed.

3 . . . phytotoxity against crops is observed.

2 . . . some phytotoxity against crops is observed.

1 . . . phytotoxity against crops is scarely observed.

0 . . . no phytotoxity against crops is observed.

                                      TABLE 3                                      __________________________________________________________________________           Applica-                                                                       tion Rice  Barnyardgrass             Scirpus                             Compound                                                                             dosage                                                                              (Orgza                                                                               (Echinochloa                                                                           Monochoria                                                                           Lindernia                                                                            Rotala                                                                               iun-                                                                               Sagittaira                                                                          Cyperus                                                                             Eleocharis            No.   (g/a)                                                                               sativa)                                                                              crus-galli)                                                                            vaginalis                                                                            procumbens                                                                           indica                                                                               coides                                                                             pygmaea                                                                             serotinus                                                                           kuroguwai             __________________________________________________________________________      1    0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      2    0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      3    0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      4    0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      8    0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      10   0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      43   0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      44   0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                      45   0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                     145   0.25 0     5       5     5     5     5   5    5    5                           0.125                                                                               0     5       5     5     5     5   5    5    5                           0.063                                                                               0     5       5     5     5     5   5    5    5                     Compara-                                                                             0.25 4     4       4     5     4     5   4    5    4                     tive com-                                                                            0.125                                                                               3     3       3     5     4     5   3    4    3                     pound D                                                                              0.063                                                                               2     2       2     4     3     4   2    3    2                     Compara-                                                                             0.25 2     5       4     5     5     5   4    5    4                     tive com-                                                                            0.125                                                                               1     4       3     4     4     4   3    4    3                     pound E                                                                              0.063                                                                               0     3       2     3     3     3   2    4    2                     Compara-                                                                             0.25 3     4       4     5     5     5   4    4    4                     tive com-                                                                            0.125                                                                               2     3       3     4     4     4   3    3    3                     pound F                                                                              0.063                                                                               1     2       2     3     4     3   2    2    2                     Compara-                                                                             0.25 3     4       4     4     5     5   4    4    3                     tive com-                                                                            0.125                                                                               2     3       3     3     4     4   3    3    2                     pound G                                                                              0.063                                                                               1     2       2     2     3     3   3    2    1                     Compara-                                                                             0.25 2     5       4     4     4     5   4    5    3                     tive com-                                                                            0.125                                                                               1     4       4     3     3     4   3    4    2                     pound H                                                                              0.063                                                                               0     3       3     2     2     3   3    3    1                     Compara-                                                                             0.25 2     5       4     4     4     5   4    5    3                     tive com-                                                                            0.125                                                                               1     4       3     3     3     4   3    4    2                     pound I                                                                              0.063                                                                               0     3       2     2     2     3   2    3    1                     Compara-                                                                             0.25 4     4       3     3     3     4   5    4    3                     tive com-                                                                            0.125                                                                               3     3       2     2     3     3   4    3    3                     pound L                                                                              0.063                                                                               2     2       1     1     2     2   3    3    2                     Compara-                                                                             0.25 2     5       3     4     4     4   4    4    3                     tive com-                                                                            0.125                                                                               1     4       2     3     3     3   3    3    2                     pound M                                                                              0.063                                                                               0     3       1     2     2     2   3    2    1                     Compara-                                                                             0.25 3     4       3     4     4     4   4    4    3                     tive com-                                                                            0.125                                                                               2     3       2     3     3     3   2    3    2                     pound N                                                                              0.063                                                                               1     2       2     2     2     2   2    2    1                     __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________          Applica-                     Pigweed                                                                             Smart-                                                                               Cocklebur                                                                            Velvet                                                                               Yellow                Com- tion Corn                                                                               Barnyardgrass                                                                          Green fox-                                                                           Crabgrass                                                                            (Amaran-                                                                            weed (Poly-                                                                          (Xanthium                                                                            leaf                                                                                 nutsedge              pound                                                                               dosage                                                                              Zea (Echinochloa                                                                           tail (Seta-                                                                          (Digitaria                                                                           thus as-                                                                            gonum strumari-                                                                            tilon                                                                                (Cyperus              No.  (Kg/ha)                                                                             mays)                                                                              crus-galli)                                                                            ria viridis)                                                                         ciliaris)                                                                            cendens)                                                                            nodosum)                                                                             um)   phrasti)                                                                             esculeutus)           __________________________________________________________________________      18  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                      19  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                      20  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                      21  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                      28  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                      41  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                      42  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                     152  0.25 0   5       5     5     5    5     5     5     5                          0.125                                                                               0   5       5     5     5    5     5     5     5                          0.063                                                                               0   5       5     5     5    5     5     5     5                     Compara-                                                                            0.5  0   5       5     5     5    5     5     5     5                     tive com-                                                                           0.25 0   4       4     4     4    4     4     4     4                     pound A                                                                             0.125                                                                               0   3       3     3     4    3     3     4     4                     Compara-                                                                            0.5  0   4       3     4     4    4     4     4     4                     tive com-                                                                           0.25 0   3       3     3     3    3     3     3     3                     pound B                                                                             0.125                                                                               0   2       2     2     2    2     2     2     2                     Compara-                                                                            0.5  0   5       4     4     5    5     5     5     4                     tive com-                                                                           0.25 0   3       3     3     3    4     4     4     3                     pound C                                                                             0.125                                                                               0   3       2     2     3    3     2     3     1                     Compara-                                                                            0.5  1   4       4     5     4    4     4     4     3                     tive com-                                                                           0.25 0   4       3     4     4    4     3     4     4                     pound J                                                                             0.125                                                                               0   3       2     3     3    3     3     3     2                     Compara-                                                                            0.5  1   4       4     4     4    4     4     4     3                     tive com-                                                                           0.25 0   3       2     4     3    3     3     3     2                     pound K                                                                             0.125                                                                               0   2       1     3     3    2     2     2     1                     Atrazine                                                                            1.0  1   3       3     2     5    5     5     4     1                          0.5  0   2       2     1     4    4     4     3     0                          0.25 0   1       1     1     4    3     3     2     0                     __________________________________________________________________________

                  TABLE 5                                                          ______________________________________                                                        Application                                                                    dosage    Corn                                                  Compound No.   (Kg/ha)   (Zea mays)                                            ______________________________________                                         18             2         0                                                                    1         0                                                     19             2         0                                                                    1         0                                                     20             2         0                                                                    1         0                                                     21             2         0                                                                    1         0                                                     28             2         0                                                                    1         0                                                     41             2         0                                                                    1         0                                                     42             2         0                                                                    1         0                                                     152            2         0                                                                    1         0                                                     Comparative    2         2                                                     compound A     1         1                                                     Comparative    2         2                                                     compound B     1         1                                                     Comparative    2         2                                                     compound C     1         1                                                     Comparative    2         3                                                     compound J     1         2                                                     Comparative    2         3                                                     compound K     1         2                                                     ______________________________________                                          ##STR18##                                                                      ##STR19##                                                                      ##STR20##                                                                      ##STR21##                                                                      ##STR22##                                                                       #STR23##                                                                      ##STR24##                                                                      ##STR25##                                                                      ##STR26##                                                                      ##STR27##                                                                      ##STR28##                                                                      ##STR29##                                                                      ##STR30##                                                                      ##STR31##                                                                 

What is claimed is:
 1. A pyrazole derivative of the formula I: ##STR32## wherein R represents an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms which may be substituted by halogen atom,X represents a halogen atom, a lower alkyl group, nitro group, cyano group, a lower alkylsulfonyl group or trifluoromethyl group, n represents an integer of 1 to 3, Q represents hydrogen atom; a carbocyclic aryl lower alkyl group which may be substituted by halogen atom, nitro group, cyano group or a lower alkyl group; benzenesulfonyl group which may be substituted by a lower alkyl group or halogen atom; benzoyl group which may be substituted by a lower alkyl group or halogen atom; phenacyl group which may be substituted by a lower alkyl group or halogen atom; a lower alkyl group which may be substituted by halogen atom; a lower alkenyl group which may be substituted by halogen atom; or a lower alkynyl group.
 2. A compound of the formula I according to claim 1, whereinR represents an alkyl group having 2 to 4 carbon atoms or allyl group, X represents a halogen atom, a lower alkyl group, nitro group, a lower alkylsulfonyl group or trifluoromethyl group, n is an integer of 1 to 3, and Q represents benzyl, tosyl, methanesulfonyl, benzoyl, phenacyl, allyl, propargyl group or hydrogen atom.
 3. A compound of the formula I according to claim 1, whereinR represents an ethyl or isopropyl group, X represents a halogen atom, a lower alkyl group or methanesulfonyl group, n represents an integer of 1 to 3, and Q represents hydrogen atom, benzyl, tosyl, mesyl, phenacyl, allyl or propargyl group.
 4. A compound according to claim 1 of the formula VI: ##STR33## wherein R represents ethyl or isopropyl group, X represents methyl group or chlorine atom and Q represents hydrogen atom or benzyl group.
 5. A compound according to claim 1 of the formula VII: ##STR34## wherein R represents ethyl or isopropyl group, X represents methyl group or chlorine atom and Q represents hydrogen atom or benzyl group.
 6. A selective herbicidal composition containing as active ingredient a herbicidally effective amount of one or more of the compounds of the formula I: ##STR35## wherein R represents an alkyl group having 2 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms which may be substituted by halogen atom, X represents a halogen atom, a lower alkyl group, nitro group, cyano group, a lower alkylsulfonyl group or trifluoromethyl group, n represents an integer of 1 to 3, Q represents hydrogen atom; a carbocyclic aryl lower alkyl group which may be substituted by halogen atom, nitro group, cyano group or a lower alkyl group; benzenesulfonyl group which may be substituted by a lower alkyl group or halogen atom; benzoyl group which may be substituted by a lower alkyl group or halogen atom; a phenacyl group which may be substituted by a lower alkyl group or halogen atom; a lower alkenyl group which may be substituted by halogen atom; or a lower alkyl group which may be substituted by halogen atom; a lower alkynyl group, together with a suitable carriers and/or other adjuvants.
 7. The composition according to claim 6, whereinR represents an alkyl group having 2 to 4 carbon atoms or an allyl group, X represents a halogen atom, a lower alkyl group, nitro group, lower alkylsulfonyl group or trifluoromethyl group, n is an integer of 1 to 3, and Q represents a benzyl, tosyl, methanesulfonyl, benzoyl, phenacyl, allyl, propargyl group or a hydrogen atom.
 8. The composition according to claim 6, whereinR represents an ethyl or isopropyl group, X represents a halogen atom, a lower alkyl group or a methanesulfonyl group, n is an integer of 1 to 3, and Q represents a hydrogen atom, a benzyl, tosyl, methanesulfonyl, benzoyl, phenacyl, allyl, or propargyl group.
 9. The composition of claim 6, whereinR represents an ethyl or isopropyl group, n is 1, X represents a methyl group or chlorine atom, and Q represents a hydrogen atom or benzyl group.
 10. The composition of claim 6, whereinR represents an ethyl or isopropyl group, n is 2, X represents a methyl group or chlorine atom, and Q represents a hydrogen atom or benzyl group.
 11. A method for damaging and controlling weeds which comprises applying to the weeds or to the locus thereof a herbicidally effective amount of a compound of the formula I claimed in claim
 1. 12. A pyrazole derivative of the formula II: ##STR36## wherein R represents an alkyl group having 2 to 4 carbon atoms or an alkenyl group which may be substituted by halogen atom. 